Light-sensitive polymeric diazonium and azidoacrylamido reproduction materials and process for making plates therefrom



United States LIGHT-SENSETIVE PQlAYMERl DIAZQNEUM AND AZlDGACRYLAMiDOREPRQDUCTEQN MATE- REALS AND PE-SCESS FOR MAKENG YPLATES THEREFROM OskarSus and Kurt Reiss, v iesbaden-liiiebrich, Germany,

assignors, by mesne assignments, to Azoplate Imperation, Murray Hill,NJ.

N Drawing. Sriginai application Feb. 25, 196%, Sex. No. 1%,887, nowPatent No. 3,174,360. Divided and this application lane 25, N64, Ser.No. 378,i27 Qlaims priority, application Germany, Feb. 25, 1959,

K 37,ll93 19 Claims. ((11. 95-43) in which R and R are alkoxy groups; Dis an azido group, or a diazonium salt group, or a diazo sulfonategroup; n is an integer greater than 1; and X is hydrogen or methyl.

Among the diazonium salt groups representing group D in the aboveformula, the diazonium chloride group, or the Zinc chloride double saltof the diazonium chloride group are preferred; alternatively, D may beanother diazonium salt, e.g., diazonium borofiuoride. A reaction of thediazonium group with sodium sulfite leads to diazo sulfonates, anotheralternative for group D.

The polymeric diazo and azido compounds of substituted acrylic acidamides are obtained by polymerizing, preferably in a solvent, acrylicacid amides which are substituted at the nitrogen atom of the amidegroup by a p-nitrophenyl radical substituted by alioxy groups in the 2-and 5-positions, using one of the conventional radicalforming agents inthe polymerization process, such as peroxide or azo compounds, e.g.,dibenzoyl peroxide, dicumene hydroperoxide, di-tert.-butyl peroxide orazoisobutyric acid dinitrile. It may be of advantage to effectpolymerization in very dilute solutions, using, e.g., suiticient solventso that the solution contains only from 1-25 percent, preferably from5-20 percent by weight, of the monomeric compound. Polymerizates whichdo not precipitate by themselves are obtained by adding a precipitatingagent or by distilling the solvent oil. The substituted polymericacrylic acid amides containing nitro groups are reduced to thecorresponding amino compounds, using, e.g., hydrogen and a metalcatalyst, such as Raney nickel. By treatment with a metal nitrite,especially with an alkali metal nitrite, such as sodium nitrite orpotassium nitrite, in an acidic solution, or with an organic nitrite,e.g., isoamyl nitrite, polymeric diazo compounds are obtained from saidpolymeric amino compounds. The corresponding polymeric azides can beprepared by the reaction of an inorganic azide with the diazoniumcompounds. In

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many cases, it is possible to facilitate precipitation of the diazoniumcompounds and obtain more stable end products by converting them intodouble salts, e.g., zinc chloride double salts, or into diazosultonates, by means of sodium sulfite.

The monomeric acrylic acid amides which carry nitrophenyl groups assubstituents at the nitrogen atom of the amide groups, are prepared bythe reaction of acrylic acid chloride with the respective amines.Instead of acrylic acid chloride, there may be used methacrylic acidchloride. It was surprising to discover that acrylic acid amidessubstituted by aromatic rings carrying nitro groups can be easilypolymerized because, in general, negative substituents at the hydrogenatom of the nitrogen atom of the amide group impede polymerization.

The polymeric diazo and azido compounds, respectively, according to thepresent invention are particularly suited for the preparation oflight-sensitive layers on suitable base materials which are to be usedfor making photomechanical reproductions.

The lightdecomposition products thereof are capable of tanning colloidsand have oleophilic character. The tanned images obtainable by exposureof the sensitized material through a master may be used for thepreparation of fiat and intaglio printing plates or screen stencils. Thenovel diazo compounds are amorphous, water-soluble, yellow compoundswhich have substantive properties, i.e., they adhere very well tocellulosic base materials such as, e.g., paper or cellulose hydratefilms, and are thus particularly suited for the production of water-fastblue prints, especially by the so-called semiwet process, in which theazo component is applied from an aqueous solution to the paper afterexposure thereof.

For the preparation of the light-sensitive layers, the diazo compounds,either in the form of their water-soluble salts or double salts, such asthe chlorides, boron fluorides, zinc chloride double salts, or in theform or" their water-soluble sulfonates, are applied by known methods tothe base materials from an aqueous solution, which in addition maycontain colloids or other additives, e.g., stabilizers. 1f asides areused, they are applied in organic solvents, e.g., alcohols. Thesolutions may be applied by means of rollers. Alternatively, the basematerial may be passed through the solution or the solution may be castor sprayed onto the base material; subsequently, the layer is dried.Suitable base materials are metal toils, e.g., aluminum, copper or zincfoils, and sheets of paper or plastics, e.g., polyamides or cellulosederivatives, such as celluuose acetate or cellulose hydrate. For thepreparation of flat printing plates, the coated base material is exposedthrough a master and then developed by treating the exposed plate withWater to which some acid has been advantageously added. In order toremove minor quantitles of the diazo compound which may have beenadsorbed by the base material, aqueous alkaline solution are used whichcontain azo components with Water-solubilizing groups.

The azo dyestufl which forms enhances the hydrophilic properties of thefoil in the unexposed areas.

lntagiio printing plates are obtained by the methods customarily appliedin photomechanical reproduction processes by a transfer of the tannedimages produced on gelatine paper onto copper plates or cylinders. Inthis process, the products of the present invention are added to thegelatine as the tanning component.

For the preparation of screen stencils, tanning images are producedanalogously to known methods on base materials consisting of screen-likemetal or other fabrics by means of the products according to the presentinvention and the unexposed parts of the layer are then removed byrinsing with water, as usual.

Blue prints may be prepared by conventional methods, either by a drydevelopment of an exposed polymeric material containing the diazocompounds according to the present invention and azo components, or by asemiwet process by which the azo component is applied to the exposedpaper.

The products according to the present invention may be used in admixturewith each other or with other lightsensitive substances.

It is one of the advantages of the polymeric diazo and azido compoundsof substituted acrylic acid amides that, in addition to their excellenttanning quality, they adhere very fast and evenly to cellulosic basematerials, such as paper or cellulose hydrate films, because of theirhydrophilic properties and that they practically lose these hydrophilicproperties and become strongly oleophilic upon exposure. This factcauses an excellent differentiation between the light decompositionproducts and the undecomposed compounds which, in turn, leads toparticularly long runs when using the compounds of the present inventionfor the production of printing plates.

The following examples describe the preparation of the polymeric diazoand azo compounds according to the present invention:

Example 1 For the preparation of the zinc double salt of polymeric 2acroylamino-hydroquinone-diethylether-S-diazoniumchloride, 18.1 parts byweight of 2-amino-hydroquinone-diethylether are dissolved in 100 partsby volume of dioxane. To this solution there are slowly added, drop bydrop, first a solution of parts by weight of acroyl chloride in 10 partsby volume of dioxane and then a solution of 12.7 parts by weight ofanhydrous sodium carbonate in 125 parts by volume of water. A weaklyalkaline reaction of the reaction mixture must be maintained.Subsequently, the mixture is heated to 70-80 C. and agitated for 2 hoursat this temperature. Thereafter, the reaction mixture is poured into 500parts by volume of water, while agitating. The precipitating2-acroylamino-hydroquinone-diethylether is separated by suction andrecrystallized from dilute alcohol. 17.5 parts by weight (=75 percent ofthe theoretical yield) of a colorless substance are obtained which has amelting point of 123 C.

For the nitration of this compound, 11.5 parts by weight of2-acroylamino-hydroquinone-diethylether are dissolved in 150 parts byvolume of glacial acetic acid. The mixture is cooled down to 10 C. andthen 9 parts by volume of nitric acid, having a density of 1.3 arecautiously added. The nitro compound is precipitated by pouring thereaction mixture into 500 parts by volume of water. For purification,the compound is recrystallized from a 1:2 mixture of alcohol and water.13 parts by weight (=94 percent of the theoretical yield) of2-acroylamino-5- nitrohydroquinone-diethylether are obtained, which hasa melting point of 108 C.

For polymerization, 10 parts by weight of2-acroylamino-S-nitrohydroquinone diethylether are dissolved in 50 partsby volume of ethyleneglycol monomethylether, 0.5 part by weight ofazoisobutyric acid dinitrile is added, and the reaction mixture isheated for 8 hours to the boiling point, with the exclusion of air bymeans of nitrogen. Subsequently the reaction mixture is cooled, thusprecipitating part of the polymerization product. Precipitation iscompleted by adding 200 parts by volume of alcohol. The polymerizationproduct is separated by suction and then washed with some alcohol inorder to remove any monomers which may be left. In this man ner, 7.8parts by weight (=78 percent of the theoretical yield) ofpoly-2-acroylamino-5-nitrohydroquinone di ethylether are obtained whichhas a melting range from 160-183" C;

In order to reduce the compound, 28 parts by weight ofpoly-2-acroylamino-S-nitrohydroquinoue diethylether are suspended in 200parts by volume of ethyleneglyco] monomethylether and then reduced toform the corre* sponding amino compound at a temperature of 100 C. andatmospheres excess pressure with hydrogen, using Raney nickel as acatalyst.

26.5 parts by weight of the amino compound (=94 percent of thetheoretical yield) are thus obtained; the compound melts in the rangefrom 150160 C.

For the production of the polymeric diazo compound, 8.5 parts by weightof po1y-2-acroylamino-5-aminohydro quinone diethylether are dissolved ina mixture consisting of 40 parts by volume of concentrated hydrochloricacid and 50 arts by volume of water and then diazotized by slowly adding8.1 parts by volume of a 40 percent aqueous sodium nitrite solution. Thereaction mixture is filtered by means of active charcoal andprecipitated in the form of its zinc chloride solution. 9 parts byweight of the zinc chloride double salt ofpoly-2-acroylaminohydroquinone-diethylether 5 diazonium chloride arethus obtained.

Example 2 For the preparation of the polymeric diazo sulfonate of2-acroylamino-hydroquinone-diethylether 5 diazonium chloride, 12.5 partsby weight of polyacroylamino-S- amino-hydroquinone-diethylether, whichhas been prepared by the method described in Example 1, are dissolved in175 parts by volume of a 1:1 mixture of water and hydrochloric acid.Some active charcoal is added to the reaction mixture which is thenfiltered, cooled to 05 C. and diazotized by adding 8.7 parts by volumeof a 40 percent sodium nitrite solution. While agitating, the solutionof the diazonium salt is cautiously added to a solution containing 79parts by weight of sodium carbonate and 6.3 parts by weight of sodiumsulfite in 350 parts by volume of water. Precipitation of the sulfonatewhich forms is completed by adding a saturated common salt solution; 18parts by weight percent of the theoretical yield) are obtained of an eggyolk colored powder.

Example 3 For the preparation of the azide ofpoly-2-acroylamino-hydroquinone diethylether-S-diazonium chloride, thepoly-2-acroylan1ino 5 amino-hydroquinone-diethylether, prepared inaccordance with Example 1, is diazotized as described in Example 2 andthe reaction mixture thus obtained is cautiously added to an aqueoussodium azide solution using 2.5 moles of the sodium azide solution permole of the diazotization mixture. The high molecular weight azide whichprecipitates is separated by suction and dried under reduced pressure.It is obtained in a quantity which corresponds to 98 percent of thetheoretical yield and forms a white powder with a brown is'h tinge whichhas no definite melting point. When heated to C. the compound decomposeswithout melting.

Example 4 For the preparation of the polymeric2-methacroylamino-hydroquinone diethylether-S-diazonium chloridecadmiumchloride double salt, 18.1 parts by weight of2-amino-hydroquinone-diethylether are dissolved in 100 parts by volumeof dioxane. To this solution there are simultaneously added slowly asolution of 11.5 parts by weight of methacroylchloride in 10 parts byvolume of dioxane and a solution of 12.7 parts by weight of anhydroussodium carbonate in 125 parts by volume of water. Care must be taken,that the reaction mixture constantly shows a slightly alkaline reaction(pH value of about 8). The mixture is subsequently heated over a bathhaving a temperature of 70-80 C. and agitated for 2 hours at thistemperature. Subsequently, the reaction mixture is poured into 500 partsby volume of ice water with agitation. The2-methacroylamino-hydroquinone-diethylether precipitates in the form ofan oily product which solidifies when left standing in ice. The isolatedraw product is digested with 18 percent hydrochloric acid. 21.5 parts byweight, corresponding to 85 percent of the theoretical yield, of thecrude product, free from diazo tizable components and having a meltingpoint of 37-38" C. are thus obtained. After recrystallization fromdilute methanol, the substance melts at 41 C.

For the introduction of the nitro group, 21 parts by weight ofZ-methacroylamino-hydroquinone-diethylether are dissolved in 150 partsby volume of glacial acetic acid. Nitration is efiected by adding, atC., a solution of 6.5 parts by weight of nitric acid (3:1.42) in 10parts by volume of glacial acetic acid. The solution thus obtained turnsyellow when heated. The nitro compound is precipitated by adding 50parts by volume of water. For purification, it is dissolved in a hotmixture of 250 parts by volume of alcohol and 50 parts by volume ofwater and filtered, with the addition of activated carbon.

Upon recrystallization, the compound forms yellow needles. 10.5 parts byweight of Z-methacroylamino-S- nitro-hydroquinone-diethylether of amelting point of 110 C. are thus obtained.

For polymerization of the nitro compound, 9.5 parts by weight of2-methacroylamino-5-nitrohydroquinone-dietbylether are dissolved in 70parts by volume of ethyleneglycol monomethylether, 0.1 part by Weight ofazosiobutyric acid dinitrile are added and the reaction mixture isheated for 7 hours to the boiling point while nitrogen is passedthrough. Subsequently, the solution is concentrated and twice digestedeach time with 100 parts by volume of alcohol in order to remove thestarting material. 2.4 parts by weight of poly-2-methacroylamino-5-nitro-hydroquinone-diethylether are thus obtained, which melts in therange of from 100-130 C.

For the reduction of the nitro compound, 2.4 parts by weight ofpoly-2methacroylamino-5-nitro-hydroquinonediethylether are dissolved in150 parts by volume of dioxane and then reduced at 90 C., by means or"hydrogen and using Raney nickel as a catalyst to form the correspondingamino compound. After the solvent has been distilled off under reducedpressure, 2.1 parts by weight of the amino compound are obtained in theform of a dark oil.

For the production of the polymeric diazo compound, 2.1 parts by weightof the oil are twice digested each with parts by volume of an aboutpercent hydrochloric acid and then diluted each time with 15 parts ofWater. After filtration, the solution is diazotized by cautiouslyintroducing 1 part by volume of an aqueous 2-nsodium nitrite solution.The reaction mixture is filtered over active carbon and thenprecipitated in the form of its cadmium double salt by adding a 10percent cadmium chloride solution. 0.6 part by weight of thepoly-Z-methacroylamine-hydroquinone-diethylether-S-diazoniumchloride-cadmium chloride double salt are thus obtained.

Example 5 lolymericZ-methacroylamino-hydroquinone-dimethylether-S-diazonium chloride, isprepared by analogy to the method described in Example 4. As describedin Example 4, a solution of 15.3 parts by weight of2-aminohydroquinone-dimethylether in 100 parts by volume of dioxane isreacted with the solutions of 11.5 parts by weight of mcthacrylchloridein 10 parts by volume of dioxane and of 12.7 parts by weight ofanhydrous sodium carbonate in 125 parts by volume of water. TheZ-methacroylamino-hydroquinone-dimethylether thus formed is contained inthe solvent layer on top. By adding ether, the aqueous layer isseparated. After removal of the starting material still present, theether layer with the dioxane content is twice extracted with 10 percenthydrochloric acid. After the solvent has been distilled off, 15.2 partsby weight of Z-methacroylamino-hydroquinone-dimethylether are obtained.In order to introduce the nitro group, 13.3 parts by weight ofZ-methacroylarnino-hydroquinone-dimethylether are dissolved in 30 partby volume of glacial acetic acid and 6.4 parts by volume of nitric acid(D:1.42), dissolved in 5 parts by volume of glacial acetic acid, areslowly added at a temperature of 25 to 30 C. The nitro compoundprecipitates in the form of brownish-yellow crystals. For purification,the crude product is recrystallized from ethanol. 7.4 parts by weight ofZ-methacroylamino-S-nitro-hydroquinone-dimethylether, of the meltingpoint of 147 C., are thus obtained in the form of yellow needles.

For polymerization, 6.3 parts by weight ofZ-methacroylamino-S-nitro-hydroquinone-dimethylether are dissolved in 60parts by volume of benzene, and 0.9 part by weight of azoisobutyric aciddinitrile is added to the solution. Under a reflux condenser and whileagitating, the yellow solution is heated for 7 hours to the boilingpoint in a nitrogen atomsphere. The polymerization product precipitatesin the form of a resin Which, contrary to the monomeric compound, isinsoluble in alcohol. After removal of the solvent there remain 5.3parts by weight ofpoly-Z-methacroylamino-5-nitro-hydroquinonedimethylether.

In order to reduce the nitro compound, 5.3 parts by weight ofpoly-Z-methacroylamino-S-nitro-hydroquinonedimethylether are dissolvedin 200 parts by volume of dioxane. fter adding 10 parts by weight ofRaney nickel, the dissolved compound is hydrated at C. in an autoclave.After filtration, the dioxane is removed by distillation under reducedpressure. 5.0 parts by weight of poly 2methacroylamino-S-amino-hydroquinone-dimethylether are thus obtained inthe form of a brown oil.

For the preparation of the polymeric diazo compound, 5.0 parts by weightof the oil are dissolved in 28 parts by volume of 18 percenthydrochloric acid and the solution is diluted with water until 60 partsby volume are obtained. The solution is filtered and then 5 parts byvolume of a Z-n-sodium nitrite solution are added at temperatures below5 C. The solution is filtered by means of active carbon and the diazocompound is precipitated in the form of its cadmium double salt byadding 35 parts by volume of a 17 percent cadmium chloride solution. 2.4parts by weight ofpoly-Z-methacroylamino-hydroquinone-dimethylether-S-diazonium chlorideare thus obtained in t1 e form of the cadmium chloride double salt.

The following examples illustrate the application of the above describedproducts.

Example 6 A commercially available paper foil, suited for the productionof printing plates, is coated with a 0.51.5 percent aqueous solution ofthe Zinc chloride double salt of the diazo compound according to Example1 and dried by means of a current of warm air. The thus sensitized foilis exposed through a master using, e.g., an arc lamp or a fluorescenttube. For development of the latent image, the foil is treated with a 1percent solution of phenylmethyl-pyrazolone-sulfonic acid in 1 percentsodium carbonate solution, which in 100 parts by volume of the liquidcontains 1 part by volume of a 0.5 percent solution of a Wetting agent(a reaction product of phenol and ethyleneoxide). Instead of thephenylrnethyl-pyrazolone-sulfonic acid just mentioned, there may be usedone of the following sulfonic acids: 2-hydroxy-naphthalene- 3,6disulfonic acid, l,8-diaminonaphthalene-3,6-disulionic acid,1-arnino-8-naphthol-2,4disulfonic acid or 1,8-dihydroXy-naphthalene-2,4-disulfonic acid. After development, the foilis briefly rinsed with water and then clamped to a printing apparatusoperating on the ofiset principle. After inking with greasy ink, thefoil may be used for printing. The prints obtained are negative withregard to the master used.

Example 7 An aluminum foil is coated with a 0.3 percent solution of thezinc chloride double salt of the diazo com pound according to Example 1in a 3 percent aqueous Example 8 A raw paper suited for the preparationof blue prints is coated with an aqueous solution containing 1.75percent of the diazo compound according to Example 7, 0.5 percent ofcitric acid, and 0.5 percent of aluminum sulfate, and dried. Afterexposure through a master, the image thus produced, which corresponds tothe master used and is of excellent fastness to humidity and diffusion,is developed with a commercially available wet developing agent whichcontains phloroglucinol as the azo component.

The other diazonium salts and double salts mentioned in the descriptionand their mixtures with each other may be similarly used for theproduction of copies by a semi-Wet process.

Example 9 0.2 part by weight of the azide ofpoly-2-acroylaminohydroquinone-diethylether-S-diazonium chloride (seeExample 3) and 2 parts by weight of polyvinyl pyrrolidone are dissolvedin 100 parts by volume of ethyleneglycol monomethylether and thesolution is coated onto an aluminum foil, one side of which has beenroughened. A latent tanning image is obtained by exposing the lightsensitive foil under a master to the light of an arc lamp. By treatingthe exposed foil with Water, the layer is removed in the unexposedareas. The image may be made visible by dyeing, e.g., with a Watersoluble dye, such as methylene blue. Development and the dyeing processmay be effected in one bath. An image is thus obtained which is negativewith regard to the master used.

Example 10 An aqueous solution containing 1.7 parts by weight of thepoly 2 methacroylamino-hydroquinone-diethylether-S-diazoniumchloride-cadmium chloride double salt, obtained according to the methoddescribed in Example 4, 0.5 percent of citric acid and 0.5 percent ofaluminum sulfate, is coated onto a raw paper customarily used for theproduction :of blue prints, and dried. After exposure under a positiveoriginal, the positive image thus obtained is developed with asoda-alkaline developer containing 2-oxy-3-naphthoic acid ethanol amide.The blue-violet copies thus obtained show no traces of bleeding of thedyestuffs.

Example 11 Analogously to the method described in Example 6, a paperprinting foil is coated with a 1.5 percent aqueous solution of poly 2methacroylamino-hydroquinonedimethylether diazonium chloride-cadmiumchloride double salt and then dried. After exposure under a negativeoriginal, the foil is wiped over with a 1 percent soda-alkaline aqueoussolution of phenylmethyl pyrazolone sulphonic acid, briefly rinsed withwater and then inked with greasy ink. A positive printing plate is thusobtained.

Alternatively, the diazo compound may be used for the production of blueprints by the method described in Example 10. For this purpose, e.g., a1.7 percent aqueous solution of poly 2methacroylamino-hydroquinone-dimethylether 5 diazonium chloride-cadmiumchloride double salt, containing also 0.5 percent of citric acid and 0.5percent of aluminum sulfate, is coated onto a raw paper customarily usedfor the preparation of blue prints. After drying, the paper is exposedunder a transparent positive original. Development of the image isadvantageously performed by means of a 1 percent soda alkaline solutionof 2,3-dihydroxy naphthalene. A positive image of a red-violet color isobtained.

It will be obvious to those skilled in the art that many modificationsmay be made within the scope of the present invention without departingfrom the spirit thereof, and the invention includes all suchmodifications.

What is claimed is:

1. A compound having the formula in which R and R are alkoxy groups, Dis selected from the group consisting of an azido group, a diazoniumsalt group and a diazo sulfonate group, n is an integer greater than 1,and X is selected from the group consisting of hydrogen and methylgroups.

2. Polymeric 2 acroylamino hydroquinone diethylether-S-diazoniumchloride zinc chloride double salt.

3. Polymeric 2 acroylamino hydroquinone diethylether-S-diazo-sulfonate.

4. Polymeric 2 acroylamino hydroquinone diethylether-S-azide.

5. Polymeric 2 methacroylamino hydroquinone diethylether-S-diazoniumchloride-cadmium chloride double salt.

6. Polymeric 2 methacroylamino hydroquinone dimethylether-S-diazoniumchloride-cadmium chloride double salt.

7. Light-sensitive material comprising a base material having a coatingthereon comprising a compound having l -C z- R1 11 in which R and R arealkoxy groups, D is selected from the group consisting :of an azidogroup, a diazonium salt group and a diazo sulfonate group, n is aninteger greater than 1, and X is selected from the group consisting ofhydrogen and methyl groups.

8. Light-sensitive material according to claim 7 in which the coatingincludes an organic colloid.

9. Light-sensitive material according to claim 7 in which the coatingcomprises polymeric 2-acroy1aminohydroquinone diethylether 5 diazoniumchloride zinc chloride double salt.

10. Light-sensitive material according to claim 7 in which the coatingcomprises polymeric2-acroylaminohydroquinone-diethylether-S-diazo-sulfonate.

11. Light-sensitive material according to claim 7 in which the coatingcomprises polymeric 2-acroylaminohydroquinone-diethylether-S-azide.

12. Light-sensitive material according to claim '7 in which the coatingcomprises polymeric 2-methacroylaminohydroquinone-diethylether-S-diazonium chloridecadmium chloride doublesalt.

13. Light-sensitive material according to claim 7 in which the coatingcomprises polymericZ-methacroylamino-hydroquinone-dimethylether-S-diazonium chloridecadmiumchloride double salt.

14. A process for exposing and developing light-sensitive material whichcomprises exposing a supported lightsensitive layer to light under amaster and treating the exposed layer with a developer, the layercomprising a compound having the formula in which R and R are alkoxygroups, D is selected from the group consisting of an azido group, adiazonium salt group and a diazo sulfonate group, n is an integergreater than 1, and X is selected from the group consisting of hydrogenand methyl groups.

15. A process according to claim 14 in which the compound is polymeric2-acroylamino-hydroquinone-diethylether-S-diazonium chloride zincchloride double salt.

16. A process according to claim 14 in which the compound is polymeric2-acroylamino-hydroquinone-diethylether-S-diazo-sulfonate.

17. A process according to claim 14 in which the compound is polymeric2-acroylamino-hydroquinone-diethylether-S-azide.

18. A process according to claim 14 in which the compound is polymeric2-methacroylamino-hydroquinonediethylether-S-diazoniurn chloride-cadmiumchloride double salt.

19. A process according to claim 14 in which the compound is polymeric2-methacroylamino-hydroquinonedimethylether 5 diazonium chloride-cadmiumchloride double salt.

References Cited by the Examiner UNITED STATES PATENTS 1,934,011 11/1933Schmidt et al. 9675 2,063,832 12/1936 Werner 9649 2,274,551 2/1942Kenyon et al 96-115 X 2,405,523 8/1946 Sease et al 96-75 3,016,2981/1962 Sanders et al 9691 X NORMAN G. TORCHIN, Primary Examiner.

1. A COMPOUND HAVING THE FORMULA
 14. A PROCESS FOR EXPOSING ANDDEVELOPING LIGHT-SENSITIVE MATERIAL WHICH COMPRISES EXPOSING A SUPPORTEDLIGHTSENSITIVE LAYER TO LIGHT UNDER A MASTER AND TREATING THE EXPOSEDLAYER WITH A DEVELOPER, THE LAYER COMPRISING A COMPOUND HAVING THEFORMULA